JPS59230049A - Low gas permeability polyester composition and products thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Background of the Invention The present invention relates to thermoplastic polyester compositions that are characterized by low permeability to water and carbon dioxide and exhibit good processability. More particularly, the present invention relates to thermoplastic compositions comprising ultra-high molecular weight poly(1,4-butylene terephthalate) and a modifier thereto, the modifier comprising an amorphous copolyester copolymer. This copolymer is derived from a glycol moiety and an acid moiety, and the glycol moiety is composed of 1,4-cyclohexane dimetatool and ethylene glycol in a molar ratio of 1:4 to 4:1.
The acid portion consists of at least one aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid, and mixtures of these two acids.

The invention also relates to thermoformed barrier films comprising or incorporating these compositions.

It also relates to barrier laminates and barrier containers.

It is currently known to use certain high molecular weight thermoplastic polyesters, particularly poly(ethylene terephthalate), to produce thermoformed barrier containers, such as carbonated soft drink bottles. These barrier containers are typically made from so-called "bottle grade" poly(ethylene terephthalate);
Echire:yf V71'V-)) is generally 7 x
) -/I/ / month, 2 60 ethane (60740)
α72-1174 dl when measured at 30°C in the mixture
/t. Barrier containers made from "bottle grade" poly(ethylene terephthalate) weigh only a tenth of the weight of glass, but can withstand internal pressures of 100 pounds per square inch and are rather resistant to carbon dioxide. It is transparent. These bottles are made in large quantities by thermoforming techniques such as blow molding, coextrusion blow molding, coextrusion followed by thermoforming, and co-injection blow molding.

More specifically, a bottle-like amorphous transparent glossy hollow container blow molded from a composition comprising polyethylene terephthalate is described in U.S. Pat. No. 4,745,150.

The polyethylene terephthalate composition used in this patent is trifluoroacetic acid/methylene chloride (75/2
5) 0.80 to 1.3 when measured at 30°C in the mixture
An oligomer having an intrinsic viscosity of 0 and containing (a) at least about 97% of the polymer ethylene terephthalate repeating units of the formula:

commercial grade polyethylene terephthalate, diethylene glycol and other ester-forming components, or (
b) Ethylene terephthalate copolymers containing up to about 10 moles of other dissimilar glycol and/or carboxylic acid ester forming reactants.

U.S. Pat. No. 5,822,352 discloses that the acid component is at least 80 moles of terephthalic acid groups and the diol component is at least 80 moles of ethylene glycol groups in a phenol/tetrachloroethane (50150) mixture at 30oC. The intrinsic viscosity measured at is at least 0.7
At 0 dl/f, the crystallization temperature is at least 15
7 talate of certain polyethylene tere at 0℃, injection-
It is disclosed that it can be formed into containers such as bottles by blow molding techniques.

A somewhat chemically related polyester resin is the amorphous copolyester copolymer resin, which is generally a copolyester of ethylene glycol and 1,4-cyclo-, xane dimetatool with terephthalic acid and isophthalic acid. Although it is known that these resins can be blow molded, for certain reasons they have not been given much industrial importance in the production of barrier containers such as bottles.

Furthermore, poly(1) is another closely related thermoplastic polyester.
, 4-butylene terephthalate) resin. It is known that the walls of containers made from these resins tend to be impermeable to water vapor, and it has also been found that when the melt viscosity is higher, they exhibit better resistance to carbon dioxide permeation. ing.

In the past, poly(1,4-butylene terephthalate) was generally not widely used in blow molding because of its tendency to sag when extruded.

Specifically, when this resin is extruded, it generally has a low melt viscosity, which makes it difficult to form a molten resin bulb or parison that can be inflated with gas and expanded to fit the shape of the mold.

However, the polybutylene terephthalate resin has at least 1.05 iij/r, preferably from 1.1 to 1.4 dt when measured in orthochlorophenol at 25°C.
Polybutylene terephthalate resin can be blow molded into molded containers such as bottles if it has an intrinsic viscosity of /f and the molten resin is processed at a temperature between its melt temperature and 257°C. U.S. Patent F 8,814.786
Disclosed in the issue.

Generally, efforts have been made in these patents and others to adjust the melt viscosity of poly(1,4-butylene terephthalate) resins to make them suitable for blow molding, with limited success.

The reason for this is that in order to form a parison that can be blow molded without sagging when extruded, the melt viscosity of the resin must be increased, which poses a serious problem of processing difficulties. For example, in order to obtain a resin with a controlled melt viscosity that is fluid enough to form a parison, it is generally necessary to extrude at high temperatures, so extrusion and injection are often used before blow molding. The resin inside burned and decomposed. For this reason, even poly(1,4-butylene terephthalate) resins with controlled melt viscosity are usually not suitable for large-scale blow molding.

There is a current need for thermoplastic compositions that exhibit the excellent barrier properties of high molecular weight poly(1,4-butylene terephthalate) resins, while having processing properties suitable for use in the rapid production of blow-molded barrier containers. exists in the end. Of course, other products can also be manufactured using various thermoforming techniques.

SUMMARY OF THE INVENTION Surprisingly in view of the foregoing, blow moldable thermoplastic compositions have been developed that exhibit excellent barrier properties, including good processability and low permeability to carbon dioxide and water vapor. , 4-butylene terephthalate) resin and a modifier selected from certain amorphous copolyester copolymer resins.

Add the above modifier to ultra-high molecular weight! It has been discovered that when added to J (1,4-butylene terephthalate) resins, a thermoplastic composition is obtained which has excellent barrier properties and can be thermoformed into articles useful even in high speed blow molding techniques.

The compositions of the present invention are suitable for forming barrier films and containers that exhibit better carbon dioxide permeation resistance and also exhibit other useful physical properties compared to "bottle grade" poly(ethylene terephthalate) resins. It is useful in itself.

Furthermore, it has been unexpectedly discovered that the compositions of the present invention are uniquely suited for incorporation into multi-wall barrier laminates and multi-wall barrier containers. These laminates and containers are comprised of at least one layer of the barrier composition of the present invention and at least one layer of another thermoplastic backing or resin composition. More particularly, in preferred multi-wall barrier laminates and multi-wall barrier containers within the scope of the present invention, the barrier composition layer of the present invention comprises at least one
It is arranged adjacent to the major surfaces of one aromatic polycarbonate resin layer, particularly preferably intermediately adjacent to the major surfaces of two aromatic polycarbonate material layers to form a sandwich structure laminate. Laminates and multi-walled barrier containers having such polycarbonate-barrier layer-polycarbonate laminate configurations have the advantage that products and containers made from these laminates are physiologically harmless and are excellent for cleaning procedures. It has some notable advantages of being durable and reusable.

Unexpectedly, these laminates incorporating the barrier compositions of the present invention can be thermoformed into strongly bonded laminates without the need for additional adhesive compositions. Previously, adhesive compositions were required to firmly bond incompatible thermoplastic resin layers together to obtain a strongly laminated material.

Additionally, the compositions of the present invention can be used to fabricate barrier containers 2, such as bottles, having desirable polycarbonate-barrier compositions with polycarbonate sidewall configurations by high speed coextrusion blow molding techniques.

Other objects and advantages of the invention will become apparent from the following detailed description of the invention, taken in conjunction with the accompanying drawings.

In its broadest sense, the present invention provides new and improved thermoplastic compositions. This composition consists of the following (a) and rb).

(a) Ultra-high molecular weight poly(1,4-butylene terephthalate) resin. This is approximately 1.5 when measured at 30°C in a phenol/tetrachloroethane (60/40) mixture.
It has an intrinsic viscosity greater than dj/f.

(b) Modifier for (a). It consists of an amorphous copolyester copolymer derived from (1) and (11) below.

(1) Glycol part. It consists of a glycol selected from 1,4-cyclohexane dimetatool and a mixture of 1,4-cyclohexanedimetatool and ethylene glycol. However, in the case of the mixture, the molar ratio of 1,4-cyclohexane dimetatool to modified ethylene glycol is about 1=4 to 4:1.

(ii) Acid part. It consists of an aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid and mixtures of these two acids. However, the glycol moiety (i) is 1.4
- °When cyclohexane dimetatool is used alone, the acid moiety is a mixture of terephthalic acid and isophthalic acid.

poly(ethylene terephthalate) resin, which may also contain units derived from cyclohexane dimetatool, is compatible with poly(1,4-butylene terephthalate) in any proportion; This poly(1,4-
Butylene terephthalate) is available over a wide molecular weight range and has a non-critical upper limit for its intrinsic viscosity, which is patented at about 2.5% when measured in a 60/40 phenol/tetrachloroethane mixture. For example, Fox (Fax) and Wampack (
Wam'bach) U.S. Patent No. 5.95”y594
Already known by No. However, particular preference has been given to the medium molecular weight range, i.e. 15 to 1
．． It has an intrinsic viscosity of 3 dl/l, and is in the ultra-high molecular weight range, such as the t s erg/y used in the present invention.
That's not all. Furthermore, the poly(ethylene terephthalate) component of the Fox and Wambach patent is said to contain "small" amounts, although it may contain units derived from cyclohexane dimetatool.

Although one such material may be used in certain types of amorphous copolyester modifiers of the present invention, the molar range of ethylene glycol to cyclohexane dimetatool used in the particular class of amorphous copolyester modifiers of
It should not be interpreted as falling within the range of :4 to 4:1. In any event, the disclosure of the Fox and Wambach patent has no bearing on melt viscosity and vapor permeability issues. These problems are advantageously solved by thermoforming the compositions of the present invention into barrier containers.

, these compositions exhibit good processability and can be used to form into articles by methods commonly used for forming thermoplastic compositions. These common methods include, but are not limited to: Namely, extrusion, coextrusion, film extrusion, profile extrusion, pipe extrusion, injection molding, injection blow molding, extrusion blow molding, extrusion coating,
Foam molding.

There are foam extrusion, thermoforming, and other multi-step processes.

For example, there are film coextrusion followed by thermoforming, extrusion-coinjection blow molding, and more specifically, 2 and 3 described below.
There are 0 cases. The compositions of the present invention can be conventionally processed without the difficulties encountered in the past when attempting to process high molecular weight poly(1,4-butylene terephthalate) resins.

The compositions of the invention exhibit good processability over a wide composition range, good physical properties, and excellent barrier properties demonstrated by low permeability to carbon dioxide and water vapor.

In general, but not limited to, useful compositions having the above characteristics include an ultra-high molecular weight poly(1° 4-butylene terephthalate) resin (referred to as component (a)) and an amorphous copolyester copolymer modified The composition obtained is about 98 to 2 parts by weight of component (a) and about 2 to 98 parts by weight of component (1+) per 100 parts of the total weight of the agent (referred to as component (1+)). However, in a preferred embodiment, the composition of the invention comprises:
Total 100 parts by weight of (a) and (b) approximately 20 to 80 parts by weight
Contains parts by weight of component (1,).

The compositions of the invention may optionally contain impact modifiers.

It may also contain flame retardants, reinforcing agents, fillers, pigments, etc.

Ultra-high degree of polymerization, i.e. ultra-high molecular weight poly(1,4-butylene terephthalate) used as component (a) of the present invention
The resin generally consists of a saturated condensation product of 1,4-butanediol and an aromatic dicarboxylic acid, primarily terephthalic acid or its derivatives. Although the resin may be branched and crosslinked, for example through chemical bonds or by other known methods, the resin with branches may not be suitable for the molding process of the ultra-high molecular weight resin used in the present invention. This is not preferred since very viscous polymerization mixtures often have to be handled when doing so. It should be understood that the poly(1,4-butylene terephthalate) resin may contain small amounts of cycloaliphatic linkages, such as those derived from 1,4-cyclohexane dimetatool. In addition to the terephthalic acid units, other dicarboxylic acids such as adipic acid, naphthalene dicarboxylic acid, isophthalic acid and ortho-phthalic acid may be used, for example from about α5 to about 15 moles of total acid units. The alkylene components can be similarly varied, including ethylene glycone-propylene glycol, 1,5-pentadiol,
It may contain units derived from 1,6-hexanediol, 1,10-decanediol, alicyclic diol, mixtures thereof, and the like. Preferably, the alkylene units contain 2 to 6 carbon atoms, and in particular 1,4-butylene units are particularly preferred alkylene units since they result in polyesters that crystallize very rapidly from the melt.

Methods for making such polyesters are well known to those skilled in the art. Generally, terephthalic acid or ester and excess alkylene glycol are mixed in the presence of a conventional polyester catalyst, the mixture is then heated to form a prepolymer, and the prepolymer is then Heat under high vacuum until a normally high degree of polymerization is achieved. These methods are described in U.S. Patent No. 2,465,31
No. 9, No. &047.539 and No. 692,744
It is cleverly written in the issue. All of these patents are incorporated herein by reference.

Whether branched or not, it is essential to produce component (a) higher than the normal molecular weight range.

In general, the ultra-high molecular weight compounds used in the present invention! J (1,4
-butylene terephthalate) resins have an intrinsic viscosity of greater than about 1.5 dt/f when measured at 30° C. in a phenol/tetrachloroethane (60/40) mixture.

Poly(1,
Particularly good results are obtained with 4-butylene terephthalate), which has a concentration of about 55. Q Approximately corresponds to the molecular weight of OO. Polymerization in this ultra-high molecular weight range is not easily achieved by conventional procedures, but means are known to achieve it, such as solid state polymerization techniques.

゛Ultra high molecular weight polymer used in the present invention! A particularly preferred and convenient method of forming the IJ (1,4-butylene terephthalate) resin is to prepare a polyJ (1,4-butylene terephthalate) resin of conventional molecular weight, e.g., with an intrinsic viscosity of about 1.1 dt/f. , re-extrusion at about 2 at' to 270 DEG C. with a small amount, about 1 weight, of sodium carbonate catalyst. This method increases the melt viscosity and intrinsic viscosity into the ultra-high molecular weight range used in this invention. Detailed information regarding similar methods of forming ultra-high molecular weight polyesters and suitable catalysts can be found in U.S. Pat. No. 4.3 to Lu et al.
No. 51.758 and Japanese Patent No. 46,646 (19
1973), these are chemical abstructs (Chemical abstracts) 81
: 4492 #4485f (1974) provides an overview. Both of these patents are incorporated herein. This method will be explained in more detail in the Examples below.

The amorphous cobolye dimethyl copolymer used as modifier component (b) in the present invention is generally, but not limited to, 1,4-cyclohexane dimetatool alone or 1,4-cyclohexane dimetatool alone or
．． A glycol part consisting of a mixture of 4-cyclohexane dimetatool and ethylene glycol (however, the molar ratio of 1.4-cyclohexane dimetatool and ethylene glycol is approximately 1 = 4 to 4:1), and terephthalic acid, isophthalic acid, or both. A copolyester derived from an acid moiety consisting of a mixture of acids. However, when the glycol part consists only of 1,4-cyclohexane dimetatool, a mixture of terephthalic acid and isophthalic acid is used in the acid part of the copolyester.

Polyester copolymer component (b) can be prepared by methods well known to those skilled in the art, such as condensation reactions substantially as described and illustrated in US Pat. No. 2,901,466. More particularly, one or more acids or acid mixtures or one or more alkyl esters of aromatic dicarboxylic acids, such as dimethyl terephthalate, are placed in a flask together with one or more dihydric alcohols to initiate the condensation of the copolymer. temperature sufficient to, e.g. 15
0° to 2: Heat to 25°C. Then reduce the temperature to about 250
The temperature was raised to 30°C to 300°C, and the pressure was reduced until the condensation reaction proceeded almost completely.

The copolyester used as component (b) in the present invention is:
Typically, 60/40 phenol/tetrachloroethane or similar other solvents have an intrinsic viscosity of at least about 0.4 tU/t when measured at about 30°C. The relative amount of 1,4-cyclohexane dimetatool to ethylene glycol in the glycol portion is such that the molar ratio of 1,4-cyclohexane dimetatool to ethylene glycol is 1:4 to obtain a polyester copolymer with suitable properties. As long as it becomes ~4:1, it can be changed. This allows less destructive processing conditions and lower molding temperatures to be used when producing molded articles from the compositions of the invention. A copolymer having a composition within the above range is useful when it is desired to lower the heat distortion temperature of the ultra-high molecular weight polymer component (a). This is because the addition of small amounts of these copolymers does not affect other desirable physical properties, particularly permeability, even though the overall processing temperature of the composition is significantly lowered.

Preferred copolymers for use as component (b) in the present invention include those cocolymers containing more 1,4-cyclohexane dimetatool than ethylene glycol, e.g.
1,4-cyclohexane dimetatool and 35 moles (fraction) of 1,4-cyclohexane dimetatool greater than the o/so mixing ratio, particularly preferably about 65 moles (fraction)
A copolymer consisting of a glycol moiety having a molar C fraction of ethylene glycol) and an acid moiety of terephthalic acid.
, 4-butylene terephthalate), the resulting blends are generally compatible over a wide range of components and exhibit a single glass transition temperature, i.e., a single phase blend is formed; The blend exhibits excellent clarity. Commercially available copolyesters of this preferred type are manufactured by Eastman Chemical Company.
(Eastman Ohemlca100mpan7
)'s Eftal (KKTAR) POTG.

Other preferred polyesters for use as component (b) in the present invention are those in which the glycol moiety has more ethylene glycol than 1,4-cyclohexane dimetatool, e.g. greater than so/so, particularly preferably 1 ．．
The copolyester is composed of about 70 moles of ethylene glycol per 30 moles of 4-Schiff tetrahexane dimetatool, and the acid moiety is terephthalic acid. When this preferred copolyester is pre-predated with an ultra-high molecular weight polyester in a wide range of proportions, the resulting composition is
It exhibits excellent strength and excellent resistance to water or carbon dioxide permeation. A preferred copolyester of this type is also commercially available from Eastman Chemical Company under the trademark KODAR PIItTG 6765.

Yet another preferred amorphous copolyester copolymer is
1,4-Cyclohexane dimetatool and isophthalic acid-
It is a reaction product obtained by condensing a terephthalic acid mixture. This amorphous copolymer may be prepared as described above or as described in US Pat. No. 4.18 al. 54, incorporated herein by reference. Generally, the preferred copolymers contain a mixture of 10-25% by weight of isophthalic acid and 90-75% by weight of terephthalic acid.
- Obtained by condensation with cyclohexane dimetatool.

This type of Kobolimaha used in the present invention is KODAR A from Eastman Chemical Company.
It is marketed under 150 trademarks.

The compositions of the present invention are manufactured by methods well known in the art. Usually, ultra-high molecular weight Bo! J (1,4-butylene terephthalate) and the copolyester copolymer are blended in an extruder with impact modifiers (if used), flame retardants, blowing agents, reinforcing agents, pigments and/or stabilizers, and then Extrude and form into pellets. Thereafter, it may be processed and thermoformed into useful molded articles using conventional methods such as those described above.

These compositions are particularly useful in forming products where both good physical properties and low gas permeability are desired, such as barrier films, barrier laminates, and barrier containers. Importantly, the compositions of the present invention can be formed into barriers, films and barrier containers by high speed blow molding techniques. That is, completely unrecognized by Fox and Wambach, U.S. Pat. (1,4-butylene terephthalate)
It has now been discovered that polyesters derived from ethylene glycol and terephthalic acid can be made from low blow moldable compositions.

In this aspect, the present invention relates to a new and improved barrier film and barrier container 1, such as a bottle for carbonated soda.
The container exhibits improved barrier properties to water vapor and carbon dioxide permeation and is thermoformed from a thermoplastic composition consisting of (, L) and (b) below.

(a) Ultra-high polymerization degree poly(1,4-butylene terephthalate) resin. This resin is about 1.0% when measured at 50°C in a 60/40 mixture of phenol/tetracroμethane.
5 a 7' It has a larger intrinsic viscosity than f.

(b) Modifier for (a). This is the following (i)
and (11).

(1) Glycol part. This is ethylene glyco-#,
1.4-Cyclohexane dimetatool, and 1゜4-
The glycol is selected from a mixture of cyclohexane dimetatool and ethylene glycol.

However, in the case of the above mixture, the molar ratio of 1,4-cyclohexane dimetatool and ethylene glycol is about 1:4 to 4.
:1.

(ii) Acid part. This is an aromatic dicarboxylic acid selected from terephthalic acid, isophthalic acid and mixtures of both acids. However, when the glycol portion (i) consists of 1°4-cyclohexanedimetatool alone, the acid portion is a mixture of terephthalic acid and isophthalic acid.

These new and improved barrier films and barrier containers are advantageously manufactured by expansion speed blow molding techniques. However, other thermoforming techniques may also be used, such as injection molding.

The major steps in blow molding the new and improved barrier container of the present invention are schematically illustrated in FIG. Generally, this process involves three main steps.

It can be described separately into B and C. In step A, the new and improved thermoplastic barrier composition of the present invention is injected into a preform mold to form a parison. In the process, the parison is transferred to a preheated blow molding mold, where inflation gas is introduced into the inside of the parison to inflate the parison and collapse it against the inner wall of the blow molding mold. This gives the parison the shape of a bottle. Thereafter, in step C, the formed parison is cooled to produce the new and improved barrier container of the present invention. The container is then removed from the molding machine and stored until use.

More particularly, as shown in step A of FIG.
It is formed by injecting from the die 12 into the preforming mold 16. The preforming mold 16 is typically a split mold, which surrounds the periphery of a cylindrical mandrel 18. When the composition 10 is extruded or injected into the heated preform mold 16, the space between the mandrel 1B and the inner wall of the preform mold 16 is filled with the thermoplastic composition 10, forming the parison 2o. It has a hollow cylindrical shape. Preforming mold 1
Within 6, the parison 2o may be provided with a neck structure, such as the illustrated screw 22, and the bottom of the parison 2o is normally closed and sealed (not shown).

The mold halves 16 are then separated, usually by hydraulic or pneumatic means, and the preformed, still molten parison 20'
is transferred to step B using a mandrel 18. In process B, the split mold 26 for blow molding is used to hold the preformed parison 20'.
It surrounds. The interior surface of the blow mold 26 is designed to provide the final shape of the barrier container being molded, in this case a bottle. To blow-mold the molten preformed parison 20' located within the blow-molding mold 26 into the shape of a bottle, an inert gas, such as nitrogen, is blown into the interior of the parison 20' to inflate and expand the molten parison. Usually, a small gas outlet appropriately placed in the blow molding die 2-6 is used for this purpose, but in the apparatus shown in step B of the figure, the gas outlet C1tri? y
)” v s-18 (D 81#, K G two c
@ (7)"? They are arranged radially on the line 28 close to the neck of the preformed parison 20' as shown in A and B. As shown in FIG. The gas blown radially outward from point 28 causes the preform nozzle to expand until the top of the parison 20' adjacent to the neck portion 22 expands radially outward until it abuts inside the blow mold.
Inflate G'. After that, the gas
As the mandrel 1B continues to inflate, the outward radial expansion of the parison 20' progresses along the length of the mandrel 1B, as indicated by arrow 32.

Continue expanding the parison until the outer surface of the parison matches the inner surface of the blow mold 26 and the parison 20' takes the shape of a bottle. At this point, begin cooling the blow mold and the parison. However, the pressure of the inflation gas remains constant as the bottle loses its shape during cooling and hardening.

After the fully formed parison 20' has cooled to a truly rigid, hardened shape, the blow mold mold 26 is divided and the blow mold bottle 34 is transferred for further cooling, injection and storage.

Industrially, blow molded bottles or other barrier containers are manufactured in large quantities in high speed equipment. For example, in extrusion blow molding, barrier containers, such as bottles, may be manufactured in a continuous extrusion transfer facility where a single manifold die head is used to produce multiple blow molds after cutting to the appropriate length. A hollow tube is formed so that it is continuously supplied into the mold. Another method used industrially is the continuous extrusion preform transfer process, such as the one shown in Figure 1, in which the extruded tube is placed in a forming or preforming mold. With the bottom closed or sealed and the neck open around the mandrel, the preformed molten parison is then placed in a blow mold to give it its final shape.

Other continuous methods use equipment having a vertical rotating plate or endless belt placed against the die of a continuous tube extruder and carrying a series of blow molding mold halves.

Each of these molds is independently hydraulically or pneumatically operated. As the rotating plate rotates, one mold passes under the die of the extruder once, receiving and retaining the molten cheap parison. The rotation of the vertical rotating plate or mold support carrier is set such that the open mold is maintained for sufficient time to receive the cheap, then blow mold, cool and eject the final product. has been recorded.

Whichever method is used, barrier containers made from the compositions of the present invention exhibit improved resistance to carbon dioxide and water vapor transmission and permeation compared to "bottle grade" poly(ethylene terephthalate). resistance, which makes it highly desirable for the transportation and storage of certain substances, such as carbonated shift drinks.

The invention also includes new and improved barrier films or sheets made from the compositions of the invention. Films and thick sheets may be made, for example, by extruding the thermoplastic compositions of the invention directly into nibs formed between two heated calender rolls separated by the desired thickness. Thereafter, the film or sheet is cooled, wound into rolls or cut and stored in a manner well known to those skilled in the art.

Blow-molded barrier films can also be made in large quantities from the compositions of the invention in the same manner as blow-molded pins. More specifically, a molten parison of the thermoplastic composition of the present invention is formed in an extruder die with radial air outlets, and the molten parison is stretched and expanded with gas to a length of 4 feet and a diameter of 3 feet. Form into a large blown cylindrical bubble that is larger than one fibre. The top and bottom of the blow molded parison are removed and one side of the resulting blown cylindrical film is cut open to yield a square piece of polymer film. The edges of this square section are then joined under heat and pressure with the edges of another piece of film, after which it is cooled and rolled up for storage. These can also be done according to methods known in the art.

In yet another aspect of the invention, new and improved multi-wall barrier laminates and multi-wall barrier containers are provided. these are,
It consists of at least one layer made of the composition of the invention and at least one further layer of a dissimilar thermoplastic material firmly adhered to this first layer. What are different thermoplastic materials?
It refers to a layer of thermoplastic composition that is not identical to the new and improved barrier composition of the present invention described above. Examples of these are poly°(alkylene terephthalate).

Polycarbonate, poly(arylsulfone).

Polyacrylate, polymethacrylate, polyurethane, polyamide, polyimide, polyamideimide, polyesterimide, polyesteramide.

Examples include thermoplastic elastomers. The choice of dissimilar thermoplastic materials is not critical and will depend on the desired end use of the multi-walled barrier laminate or multi-walled barrier container. Contrary to what has been pointed out in the past, the compositions of the present invention have good compatibility with different types of resins.

In a preferred embodiment of this aspect of the invention, the new and improved multi-wall barrier laminate and multi-wall barrier container are in the form of a sandwich construction. This sandwich structure comprises two outer layers of aromatic polycarbonate and a new and improved low gas permeable ultra-high molecular weight poly(1,4-butylene terephthalate) modified as disclosed herein.
It consists of an intermediate layer of resin.

Aromatic polycarbonate resins used in preferred multilayer laminates and multiwall barrier containers have repeating units of the formula:

Todoroki O where each -R- is selected from phenylene, halo-substituted phenylene and alkyl-substituted phenylene, and A and B
are each selected from hydrogen, a hydrocarbon group containing no aromatic unsaturation, and a group forming a cycloalkane group together with the adjacent -♂- atom, and the total number of carbon atoms of A and B is 12
That's it.

The aromatic carbonate polymers used in this invention are well known, and many suitable examples of such resins can be found in the Polymer Science and Technology Encyclopedia.
oped1a of Polymer 5cle
nce and TechnoIHgy) J + 1st
Volume 0, pp. 710-727.

15'69. engineering interscence of New
No. 4,054,016 to York and Baron et al. These documents are incorporated herein by reference.

The polymenobonate is preferably a high molecular weight polymer having the formula:

where R1 and R1 are hydrogen, (lower) alkyl or phenyl, and n is at least 30. Preferably 40
~400. "(Lower)alkyl" means a hydrocarbon group having 1 to 6 carbon atoms.

The high molecular weight thermoplastic aromatic polycarbonate referred to in the present invention has a number average molecular weight of about a000 to 200,000 or more,
Preferably homopolycarbonates, copolycarbonates and mixtures thereof having an intrinsic viscosity of about 10.0 OO to 80,000 υ and an intrinsic viscosity of [L30 to 1.0 dl/f when measured at 25°C in methylene chloride solution. I want it to be understood as meaning. This polycarbonate is derived from phenol as follows. That is, for example, 2,2-bis(4-hydroxyphenyl)
ft-pan, bis(4-hydroxyphenyl)methane,
2.2-bis(4-hy)'0*c3-methylphenyl)propane.

4.4-bis(4-hydroxyphenyl) to jl;y.

2.2-(he5.he'5'-tetrachloro-4,4'-
dihydroxyphenyl)propane 12.2-(to5.3
．． '5' -Tetrac day rho 4.4'-^toyaquin phenyl) propane.

2,2- (he5.he'5'-tetrabromo-4,4'
-dihydroxydiphenyl)furopane, (3,3'-
These include dichloro-4,4'-dihydroxydiphenyl)furopane and his(y,s'-cyclo4,4'-dihydroxydiphenyl)methane. Another dihydric phenol used for loading the polycarbonate described above is U.S. Patent No. 2.9φ
No. 9.835, No. 02a36s, No. 3.354゜1
No. 54 and No. 4.154.575.

These patents are incorporated herein by reference.

These polycarbonates can be manufactured by known methods. For example, the above documents as well as U.S. Pat. No. 3,989
．． No. 672, No. 4.081.750 and No. 4.123
．． 436, according to the method disclosed in No. 436.
The carbonate precursor may be reacted with phosgene, or transesterification methods such as those disclosed in US Pat. No. 154,008, as well as all other methods known to those skilled in the art. All of these are hereby incorporated by reference into the Cine specification.

Aromatic polycarbonates for use in the present invention also include polymers derived from dihydric phenols, dicarboxylic acids, and carbonic acids, such as those disclosed in U.S. Pat. No. 3,169,121.

Alternatively, if a carbonate copolymer or copolymer is desired rather than a homopolymer for the production of aromatic polycarbonates, the use of two or more different dihydric phenols, or the combination of a dihydric phenol and a glycol or an acid-terminated polyester or It is also possible to use copolymers with basic acids.

Branched polycarbonates such as those described in US Pat. No. 4,001,184 can also be used, as can mixtures of linear and branched polycarbonates.

Preferred polycarbonate resins are those derived from the reaction of bisphenol-A and phosgene and have 10 to 400 repeating units of the formula:

This polycarbonate has a polycarbonate content of 0.3 to t/y when measured at 25°C in methylene chloride or similar solvent.
.

Preferably, it has an intrinsic viscosity of α40 to α65 dt/f. Because it is easily available and reacts easily with phosgene, sb
Because the obtained polymer state shows very good properties,
Bisphenol-A is preferred as the starting dihydric phenol compound. Suitable bisphenoloom polycarbonates are available from the General Electric Company (G
eneral FilectrlCOompan7)
It is commercially available under the registered trademark name Kara Refsan (LBX 靜■).

The multi-wall barrier laminates and multi-wall barrier containers of the present invention exhibit a number of remarkable and unexpected properties.

The aromatic polycanibonate outer layer provides the laminate's strength and toughness, while the barrier composition intermediate layer effectively reduces the laminate's permeability to carbon dioxide and water vapor.

This laminate exhibits alternate striations or multilayer compatibility. That is,
These can be, for example, coextruded three layers and then shaped through a high temperature and pressure calender to bond the three layer fused laminate together. The laminate can be cooled, cut, thermoformed, or otherwise stressed without delamination.Alternatively, preformed sheets of polycarbonate and barrier material can be stacked together in a sandwich structure. . The thus stacked prelaminate is then heated at a temperature of about 260° to 280°C and about 2 G, 000
It can be brought to a pressure of Pal and then cooled.

When a peel strength test was performed by hand, no delamination of the specimen laminate was observed. This is unexpected considering that in the past, in order to obtain a strongly bonded laminate from incompatible resins, it was necessary to interpose an adhesive compound layer between the resin layers of the laminate. That's surprising. That is, the new and improved laminate of the present invention does not require the use of additional adhesives.

Another advantage of the multi-wall barrier containers of the present invention is that they can be molded using high speed coextrusion blow molding techniques.

Coextrusion blow molding of such multi-walled containers is currently well known to those skilled in the art. For example, FIG. 2 schematically shows the main steps in blow molding a new and improved multi-walled barrier container.

Similar to that already described with reference to FIG. 1 for single-walled barrier containers, the forming process for multi-walled barrier containers is as follows. That is, in step A, the three resin layers are coextruded together into a preform mold to form a multi-walled parison, and in step B
The preformed parison is then transferred to a blow mold, where it is inflated into the shape of a molded article, further cooled in step C, and the final multi-walled barrier container is removed and stored.

Specifically, as shown in FIG. 2, in step A, a triple-walled parison 46 is
are coextruded into preform die 48. The polycarbonate extruded from extruder 40 containing aromatic polycarbonate resin forms polycarbonate inner layer 50 of parison 46 in a specially designed preform mold 48 . The resin extruded into preform mold 48 from extruder 42 containing the new and improved polyester barrier composition of the present invention forms the middle or core barrier layer of parison 46.

The extruder 44 contains an aromatic polycarbonate resin, and the extruded resin forms the polycarbonate outer layer 54 of the parison 46 within the preform mold 48. As previously discussed, the bottom of the multi-walled parison 46 is sealed, at which point the parison is provided with a neck structure such as a screw 56. The molten multi-walled Balinone is then transferred to a blow molding mold 58 as shown in step B, where inflation gas is introduced into the parison 46 as described above to remove the parison near the neck of the preformed Balinone. The top of 46 is first expanded outward. Balinone then expands continuously outward and downward within the mold;
It matches the shape of the inner wall of the blow molding die 58. Thereafter, the bottle-shaped parison 60 is cooled while keeping the gas pressure constant until it is sufficiently hardened. The blow-molded bottle 60 is removed from the blow-molding mold, further cooled, and stored.

Bottles manufactured by the coextrusion blow molding process known to those skilled in the art, as described above, are multi-wall barrier containers with physiologically innocuous inner walls and outer surfaces, making them easy to clean and reuse. Shows high resistance.

The new and improved polyester of the present invention forming the core barrier layer provides the barrier containers of the present invention with excellent resistance to water vapor transmission as well as to oxygen dioxide compared to other materials tested. Also shows excellent permeation resistance.

In particularly preferred embodiments, the multi-walled barrier container comprises ultra-high molecular weight poly(1,4-butylene terephthalate) component (a)
and an intermediate barrier layer formed from a composition of about 25 parts by weight of (a) and about 75 parts by weight of (b) based on 100 parts by weight of the total amount of modifier (b). A multi-walled container having an intermediate barrier layer comprising the above-described range of components is transparent and recyclable for multiple uses.

In the above methods of manufacturing the new and improved products of the present invention, barrier films, single-walled barrier containers, multi-walled barrier laminates and multi-walled barrier containers, each of
48-516°C and normal mold temperature 9 e.g. 38-93°
Use C. Those skilled in the art will be able to easily adjust the molecular weight, etc. of the polyester molding material, if desired.

The composition of the present invention, the product obtained therefrom, and its properties will be explained below with reference to Examples. The following examples are provided to enable those skilled in the art to easily carry out the invention, and are not intended to limit the scope of the invention.

Example 1 Ultra-high molecular weight poly(1,4-butylene terephthalate) was produced as follows. Commercially available poly(1,4-butylene ethylene phthalate) having a melt viscosity (MV) of about 6,500 poise at 250°C and an intrinsic viscosity of about 1.1.
) ) (VAIIOXo315. Generalm
lectrtc Company) 99.0 parts by weight and 1 part by weight of sodium carbonate were dry mixed at 254°~
Extruded from a single scree compounding extruder at 271°C. The resulting product had a melt viscosity (MV) of 87,000 at 250°C, with a melt of 7 f as measured on a Toyo Seiki melt strength tester while the control was less than 1. It had strength. Intrinsic viscosity is t 742
Met. Therefore, the weight average molecular weight was calculated to be approximately 55,000.

According to the present invention, poly(([L7)ethylene-core (a s )
Modified by mixing an amorphous copolyester copolymer resin in the form of 1.4-cyclohexane dimethylene terevitrate) resin.

75 parts by weight of ultra-high molecular weight poly(1,4-butylene terephthalate) resin was mixed with poly((0,7')ethylene-co((
L 3) 1,4-Cyclohexane dimethylene terephthalate) (KODARPETG 6765. Ffa
stmanOhemlcal Company)
It was dry blended with 25 parts by weight and extruded at about 260°C to form pellets.

The pellets were then film extruded at about 232°C into a film about 7.2 mils thick. The transparency of this film was 458 cm as measured using conventional equipment.

The barrier properties of the obtained film were evaluated. Regarding water vapor permeation, A8TM H for water vapor permeation of sheet material
-96-66 (1972) standard method
atram W tester and, for carbon dioxide permeation, a Pθrmatoram C according to a similar test method, using Modern Controls (Elk
Rlvar.

(Minnesota, USA).

In detail, the water vapor permeability of the film was tested as follows. That is, the film was sealed and equilibrated on a water bath in a container. p(IrmatramW is equipped with an R detector adjacent to the water bath, i.e. below the film, across the width of the container, which converts the moisture, or relative humidity, in the container containing the water bath into a voltage. can be converted.

This voltage detector is electrically connected to a chart recorder and is capable of recording changes in voltage over time.

After equilibrating the film with the water bath at 38°C, a stream of warm dry air is passed over the outer or upper side of the film.

Start the chart recorder and record the water vapor transmission rate through the film for 24 hours. The relative humidity in the container containing the water bath after 24 hours provides a measure of the amount of water vapor that has passed through the film.

Carbon dioxide permeation was similarly measured using a sealed container containing a known volume of carbon dioxide at a known pressure and an F-R detector.

Examples 2-4 The ultra-high molecular weight poly(1,4-butylene terephthalate) produced in Example 1 was added to various amounts of KODARPET G67.
Several barrier films were made using compositions modified with 65 or poly(ethylene terephthalate). Following the method outlined in Example 1, Permatram O
The carbon dioxide permeability and water vapor permeability of the film were tested using a Permatram W test machine and a Permatram W test machine, respectively. The composition and results of the film are shown in Table 1.

Table 1: Modified ultrahigh molecular weight poly(1,4-butylene) Ultrahigh molecular weight poly(1,4-butylene 75 60 75
60 Tele 7 Tallate Poly (Ethylene Tele 7 Tallet) --254
0 characteristic thickness mil) 7.2 7.4 9.
4 zs transparency (%) 438 B
5. O5t3B7.5CO! Transparency ((¥24#/100hh”/(#/¥f) “8”
120°591.14 Barrier films made in accordance with the present invention are poly(1,4-butylene terephthalate)
(00, transparency 34.o), KODARPKT
G 6763 (Co, permeability 30.0), bottle number of poly(ethylene tele 7 thale)) (00z permeability 12.0-20.0, depending on degree of orientation), and bisphenol-A polycarbonate) (co2 Transparency 1
050) showed excellent resistance to carbon dioxide permeation. The above CO and permeability are expressed in the same units.

The new and improved barrier films of the present invention exhibited improved carbon dioxide resistance. The water vapor permeability of the compositions of the invention is very low under standard test conditions and comparable to values of other materials listed in the literature. For example, commercially available BoIJ (
The water vapor permeability of 1,4-butylene terephthalate is 4.
．． 6, KODARP BTG6763 is &0. Bottle grade poly(ethylene terephthalate) is 2.0.
Bisphenol-A polycarbonate has a water vapor permeability of 11.0.

Two barrier compositions falling within the concave circle of the present invention were prepared according to the procedure outlined in Example 1. One is the formulation of Example 1 and the second is the formulation of Example 2, more specifically ultra-high molecular weight poly(1,4-butylene terephthalate) /KodarITG 6765 75/
25 and 60/40 blend. These two types
Each of the compositions was blow molded into 12 ounce bottles on an IMPOO molding machine B13. The molding temperatures used were as follows.

Molding temperature (℃) 75/25 Blend 229 22
9 232 25060/40 blend
224 224 227 242 Each composition was successfully blow-molded to obtain a barrier bottle for carbonated beverages.

EXAMPLE 7 The 75/25 and 60/40 blend barrier compositions of Examples 5 and 6 were prepared on a conventional co-extrusion or co-injection molding machine on an Impco B13 molding machine with adjacent inner and outer resins of bisphenol-polycarbonate. May be coextrusion blow molded with layers. Polycarbonate-Barrier Composition - Bottles with a polycarbonate sidewall structure blow mold successfully and provide barrier containers suitable for carbonated beverage storage. No adhesive is required to firmly adhere the resin layers in these multi-walled barrier containers. These bottles are washable, reusable, and exhibit excellent resistance to water vapor and carbon dioxide permeation.

All patents, applications, and publications cited above are expressly incorporated herein by reference. Although the invention has been described in terms of several preferred embodiments, modifications and other modifications will be apparent to those skilled in the art from the above teachings. For example, BoIJ ((0,7) ethylene co-(Q,
5) Instead of poly((65)1.4-'7chlorohexane dimethylene y-v-y-(O,SS) ethylene terephthalate) or poly(1° (4-cyclohexane dimethylene-terephthalate-coisophthalate) can be used.

Effective amount 2 for reinforcing glass fibers, such as components (a), (b)
) and glass in an amount of 20 parts by weight per 100 parts by weight in total.

Additionally, poly(methyl methacrylate) layers can be used in place of aromatic polycarbonate layers in multi-wall barrier laminates and multi-wall barrier containers.

All such obvious changes and modifications are included within the scope and spirit of the invention as defined in the claims.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram illustrating the major steps in forming the new and improved single wall barrier blow molded container of the present invention. FIG. 2 is a schematic diagram illustrating the major steps in forming the new and improved multi-wall barrier coextrusion blow molded container of the present invention. 10... Composition of the present invention, 16.48... Mold for preforming, 18... Ma, Sidrel, 20.20', 46.
... Parison, 26.58 ... Split mold for blow molding, 5
4.60 Molded bottle, 50 Borica-bonate inner layer, 52 Core barrier layer, 54 Polycarbonate outer layer. -35(I

Claims (1)

[Scope of Claims] (1) (a) Ultra-high molecular weight poly(1, 4
(b) (i) 1,4-cyclohexane dimetatool and a mixture of 1,4-cyclohexane dimetatool and ethylene glycol (provided that 1,4-cyclohexane dimetatool vs. ethylene glycol); The molar ratio is about 1:4-4
(ii) an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, in7thalic acid, and mixtures of these two acids; (provided that when the glycol portion consists of 1,4-cyclohexanedimetatool alone, the acid portion consists of a mixture of terephthalic acid and in7thalic acid), an amorphous copolyester copolymer derived from A modifier for the resin, comprising: a thermoplastic composition comprising: a modifier for the resin; (2) Component (a) is 98 to 2 parts by weight and component (b) is about 2 to 98 parts by weight, based on 100 parts of the total weight of components (a) and (b). The thermoplastic composition according to claim 1. (3) Component (b) is poly((7)ethylene-co(a)
s) 1,4-cyclohexane dimethylene terephthalate)
The thermoplastic composition described in Section. (4) The modifier (1,) is poly((Q, 65)
1.4-Cyclohexane dimetatool-(o, SS)
The thermoplastic composition according to claim 1, characterized in that it consists of ethylene terephthalate). (5) The thermoplastic composition according to claim 1, characterized in that the modifier (b) consists of poly(1,4-cyclohexanedimethyl-ethylenetele-7-thale-co-isophthalate). (6) (a) Ultrahigh molecular weight poly(1,4
- butylene terephthalate) resin, and (b) (1) ethylene glycol, 1,4-cyclohexane dimetatool and a mixture of 1,4-cyclohexane dimetatool and ethylene glycol (provided that 1,4-cyclohexane dimetatool (11) terephthalic acid, isophthalic acid, and mixtures of these two acids. An acid moiety consisting of an aromatic dicarboxylic acid selected from the group consisting of (provided that when the glycol moiety consists of 1,4-cyclohexane dimetatool alone, the acid moiety consists of a mixture of terephthalic acid and isophthalic acid), derived from a single-walled barrier container thermoformed from a thermoplastic composition comprising: a modifier of said resin comprising a polyester made of polyester, which exhibits low permeability to carbon dioxide and water vapor; (Force) In the thermoplastic composition, components (a) and (b)
), component (a) is about 98 to 2 parts per 100 parts of the total weight of
7. A single-wall barrier container according to claim 6, characterized in that component (b) is about 2 to 98 parts by weight. (8) A single-wall barrier container according to claim 6, wherein the modifier (b) in the thermoplastic composition comprises poly(ethylene terephthalate). (9) Modifier rb) in the thermoplastic composition is poly((0
, 7) ethylene-co(o,s) 1,4-cyclohexane dimethylene terephthalate). (11 The modifier (b) in the thermoplastic composition is poly((0
,,6s) 1. 7. A single-walled barrier container according to claim 6, characterized in that the container is made of a-cyclohexane dimetatool (tL35) ethylene terephthalate). (11) The unit according to claim 6, characterized in that the modifier (b) in the thermoplastic composition consists of poly(1°4-cyclohexane dimethylenetere-7-claytocoin phthalate). Wall barrier container. (1'IJ) The thermoplastic composition according to claim 1, characterized in that the glycol portion (b)(i) further contains ethylene glycol. (131(a) Phenol/tetrachloroethane (
60/40) The intrinsic viscosity measured at SO °C in the mixture is approximately 1
．． (1)) (a) 1,4-cyclohexane dimetatool and 1,4-cyclohexane dimetatool and ethylene glycol; mixture (provided that the molar ratio of 1.4-cyclohexane dimetatool to ethylene glycol is approximately 1:4 to 4:
(ii) an acid moiety consisting of an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures of these two acids; (However, when the glycol part consists of 1,4-cyclohexane dimetatool alone, the acid part consists of a mixture of terephthalic acid and isophthalic acid.) A barrier film having low permeability to carbon dioxide and water vapor thermoformed from a thermoplastic composition comprising: Claim 13, wherein the glycol portion (b) (i) further contains ethylene glycol.
The barrier film described in section. (15) (4) (i) Ultrahigh molecular weight poly(1,
4-butylene terephthalate) resin, and (i) Ethylene glycol, 1,4-cyclohexane dimetatool and a mixture of 1,4-cyclohexane dimetatool and ethylene glycol (however, 1,4-cyclohexane dimetatool and (b) terephthalic acid, isophthalic acid, and mixtures of these two acids. (However, when the glycol part consists of 1,4-cyclohexanedimetatool alone, the acid part consists of a mixture of terephthalic acid and isophthalic acid), at least one layer of a thermoplastic composition comprising: (B) a modifier of said resin comprising a derived polyester; and at least one other layer of a thermoplastic composition comprising: Multi-layer barrier laminate consisting of one layer and exhibiting low permeability to carbon dioxide and water vapor. Claim 1, characterized in that said layer (B) consists of a layer of bisphenol-A polycarbonate. 1
The multilayer barrier laminate according to item 5. αη A thermoformed multi-walled barrier container exhibiting low permeability to carbon dioxide and water vapor and high resistance to cleaning and reuse, comprising: (A) a first container formed from an aromatic polycarbonate; layer or inner layer, (B) (D phenol/tetrachloroethane (60/
40) Intrinsic viscosity measured at 30°C in the mixture is approximately 1.5t
Ultra-high molecular weight IJ (1,4-butylene terephthalate) resin larger than U/t, and (!ri) ethylene glycol, 1,4-cyclohexane dimetatool and 1,4-cyclohexane dimetatool. A mixture of ethylene glycol (with the exception of 1.
(b) terephthalic acid, isophthalic acid, and the like; (b) terephthalic acid, isophthalic acid, and The acid moiety consists of an aromatic dicarboxylic acid selected from the group consisting of mixtures of acids of species (provided that if the glycol moiety consists of t4-cyclohexane dimetatool alone, the acid moiety consists of a mixture of terephthalic acid and isophthalic acid) ), a modifier for said resin comprising a polyester derived from; an intermediate or core barrier layer formed from a thermoplastic composition and firmly adhered to said first layer; and (0)
The container is molded from a sandwich construction comprising a third or outer layer molded from an aromatic polycarbonate and firmly adhered to the core barrier layer. 18. The multi-wall barrier container according to claim 17, characterized in that it is thermoformed by coextrusion blow molding.